DE2537684C3 - Active anti-corrosive pigments based on iron oxide - Google Patents
Active anti-corrosive pigments based on iron oxideInfo
- Publication number
- DE2537684C3 DE2537684C3 DE2537684A DE2537684A DE2537684C3 DE 2537684 C3 DE2537684 C3 DE 2537684C3 DE 2537684 A DE2537684 A DE 2537684A DE 2537684 A DE2537684 A DE 2537684A DE 2537684 C3 DE2537684 C3 DE 2537684C3
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- Germany
- Prior art keywords
- mol
- pigments
- annealing
- corrosion
- corrosive
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000000049 pigment Substances 0.000 title claims description 58
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 title description 20
- 238000000137 annealing Methods 0.000 claims description 27
- 238000005260 corrosion Methods 0.000 claims description 23
- 230000007797 corrosion Effects 0.000 claims description 15
- 229910052742 iron Inorganic materials 0.000 claims description 15
- 150000004679 hydroxides Chemical class 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 239000011701 zinc Substances 0.000 claims description 9
- 229910052725 zinc Inorganic materials 0.000 claims description 9
- 229910052791 calcium Inorganic materials 0.000 claims description 8
- 239000011575 calcium Substances 0.000 claims description 8
- 229910052749 magnesium Inorganic materials 0.000 claims description 8
- 239000011777 magnesium Substances 0.000 claims description 8
- 229910044991 metal oxide Inorganic materials 0.000 claims description 8
- 150000004706 metal oxides Chemical class 0.000 claims description 8
- 239000007858 starting material Substances 0.000 claims description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 7
- 239000003973 paint Substances 0.000 claims description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 3
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 30
- 239000011651 chromium Substances 0.000 description 22
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 16
- 235000013980 iron oxide Nutrition 0.000 description 10
- 229910052804 chromium Inorganic materials 0.000 description 9
- 239000011787 zinc oxide Substances 0.000 description 8
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical class [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 3
- 229910002588 FeOOH Inorganic materials 0.000 description 3
- 150000001242 acetic acid derivatives Chemical class 0.000 description 3
- 150000003841 chloride salts Chemical class 0.000 description 3
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 3
- QDOXWKRWXJOMAK-UHFFFAOYSA-N chromium(III) oxide Inorganic materials O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 3
- 150000004675 formic acid derivatives Chemical class 0.000 description 3
- 150000002506 iron compounds Chemical class 0.000 description 3
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 3
- 150000002823 nitrates Chemical class 0.000 description 3
- 150000003891 oxalate salts Chemical class 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- BFGKITSFLPAWGI-UHFFFAOYSA-N chromium(3+) Chemical compound [Cr+3] BFGKITSFLPAWGI-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000001023 inorganic pigment Substances 0.000 description 2
- 239000011872 intimate mixture Substances 0.000 description 2
- 239000001034 iron oxide pigment Substances 0.000 description 2
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- JHWIEAWILPSRMU-UHFFFAOYSA-N 2-methyl-3-pyrimidin-4-ylpropanoic acid Chemical compound OC(=O)C(C)CC1=CC=NC=N1 JHWIEAWILPSRMU-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910017060 Fe Cr Inorganic materials 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- WVYYHSKIGBEZCQ-UHFFFAOYSA-N [O-2].[O-2].[Cr+3].[Fe+2] Chemical compound [O-2].[O-2].[Cr+3].[Fe+2] WVYYHSKIGBEZCQ-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- -1 aromatic nitro compounds Chemical class 0.000 description 1
- 244000052616 bacterial pathogen Species 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001845 chromium compounds Chemical class 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical class [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 1
- 239000012154 double-distilled water Substances 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- GQKCRUJOPUHISR-UHFFFAOYSA-M potassium;dizinc;dioxido(dioxo)chromium;hydroxide Chemical compound [OH-].[K+].[Zn+2].[Zn+2].[O-][Cr]([O-])(=O)=O.[O-][Cr]([O-])(=O)=O GQKCRUJOPUHISR-UHFFFAOYSA-M 0.000 description 1
- 239000001054 red pigment Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- PXLIDIMHPNPGMH-UHFFFAOYSA-N sodium chromate Chemical compound [Na+].[Na+].[O-][Cr]([O-])(=O)=O PXLIDIMHPNPGMH-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/22—Compounds of iron
- C09C1/24—Oxides of iron
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/34—Compounds of chromium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
- C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Compounds Of Iron (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Paints Or Removers (AREA)
Description
1515th
Aktive Korrosionsschutzpigmente, denen große praktische Bedeutung zukommt, sind Bleimennige, Zinkkaliumchromat und Zinkstaub. Im Vergleich zu den v> in großen Mengen verwendeten, für den Korrosionsschutz im wesentlichen inaktiven Eisenoxidpigmenten haben die erwähnten aktiven Korrosionsschutzpigmente entweder ein wesentlich höheres spezifisches Gewicht oder sind erheblich teurer. Es hat nicht an « Bemühungen gefehlt, auf der Basis der wohlfeilen und relativ spezifisch leichten Eisenoxidrohstoffe aktive Korrosionsschutzpigmente herzustellen. So wurde schon versucht, durch Zusammenglühen von Zink- und Erdalkalioxiden, -hydroxiden und -carbonaten mit m> verschiedenartigen Eisenverbindungen (Oxid, Ox id hydroxid, Carbonat, Sulfat usw.) bei Temperaturen von 650 bis 1I5O°C neue Korrosionsschutzpigmente auf Eisenoxidbasis herzustellen. Bei der AbprUfung dieser Pigmente auf ihre Korrosionsschutzwirkung zeigte sich i>> aber, daß sie im Vergleich zu handelsüblichen Eisenoxidpigmenten zwar eine geringe Verbesserung bringen, daß sie aber bei weitem nicht an die eingangsActive anti-corrosive pigments, which are of great practical importance, are red lead, zinc potassium chromate and zinc dust. , Used in comparison to the v> in large quantities for corrosion protection essentially inactive iron oxide pigments have mentioned active anticorrosion pigments either a much higher specific weight or are considerably more expensive. There has been no lack of efforts to produce active anti-corrosive pigments on the basis of inexpensive and relatively light iron oxide raw materials. Attempts have already been made to produce new anti-corrosion pigments based on iron oxide by annealing zinc and alkaline earth oxides, hydroxides and carbonates with various iron compounds (oxide, oxide hydroxide, carbonate, sulfate, etc.) at temperatures of 650 to 150 ° C. When these pigments were tested for their anti-corrosive effect, it was found that, compared to commercially available iron oxide pigments, they bring about a slight improvement, but that they are by no means as good as the one introduced at the beginning erwähnten aktiven Korrosionsschutzpigmente heranreichen. Die deutsche Auslegeschrift 12 96 291 befaßt sich mit der Herstellung femtejliger Eisenoxid-Chromoxid-MischkristalJpigroente, die durch Glühen der Chrom(III)- und Eisen(III)-Mischhydroxide bei Temperaturen von 500 bis 900° C entstehen. Auch diese Pigmente zeigen noch unbefriedigende Eigenschaften für den Korrosionsschutz,mentioned active anti-corrosive pigments. The German Auslegeschrift 12 96 291 concerned deals with the production of iron oxide-chromium oxide mixed crystals, which are obtained by annealing the Chromium (III) and iron (III) mixed hydroxides are formed at temperatures of 500 to 900 ° C. These too Pigments still show unsatisfactory properties for corrosion protection,
Aufgabe der vorliegenden Erfindung ist die Entwicklung aktiver Korrosionsschutzpigmente auf Eisenoxidbasis, die hinsichtlich ihrer Korrosionsschutzwirkung den bekannten aktiven Korrosionsschutzpigmenten ebenbürtig sind und die Nachteile der bekannten Korrosionsschutzpigmente nicht aufweisen.The object of the present invention is to develop active anti-corrosive pigments based on iron oxide which, with regard to their anti-corrosive effect are on a par with the known active anti-corrosive pigments and have the disadvantages of the known ones Do not have anti-corrosive pigments.
Gegenstand der vorliegenden Erfindung sind Korrosionsschutzpigmente, bestehend aus 30 bis 70 Mol-% MeO und 70 bis 30 Mol-% Fe2O3, wobei 0,1 bis zu 20 Mol-%, vorzugsweise 0,1 bis 10 Mol-%, besonders bevorzugt 0,2 bis 5 Mol-%, des Fe2O3 durch die entsprechende molare Menge Cr2O3 ersetzt sind und wobei Me for Magnesium, Calcium, Zink, die auch in beliebigen Kombinationen vorhanden sein können, steht, mit einer spezifischen Oberfläche zwischen 1 bis 30 m2/g nach BET, welche durch Glühen der entsprechenden Metalloxide oder der beim Glühen derartige Metalloxide ergebenden Ausgangsstoffe erhalten worden sind, wobei die Glühung bei Temperaturen von 200 bis 9000C durchgeführt worden istThe present invention relates to anti-corrosive pigments consisting of 30 to 70 mol% MeO and 70 to 30 mol% Fe 2 O 3 , 0.1 to 20 mol%, preferably 0.1 to 10 mol%, in particular preferably 0.2 to 5 mol% of the Fe 2 O 3 have been replaced by the corresponding molar amount of Cr 2 O 3 and Me stands for magnesium, calcium, zinc, which can also be present in any combination, with a specific surface area of between 1 to 30 m 2 / g by BET, which output substances resulting by annealing the corresponding metal oxides or metal oxides such during annealing have been obtained has been wherein the annealing at temperatures of 200 to 900 0 C performed
Gegenstand der vorliegenden Erfindung ist ferner ein Verfahren zur Herstellung von Korrosionsschutzpigmenten, bestehend aus 30 bis 70 Mol-% MeO und 70 bis 30 Mol-% Fe2O3, wobei 0,1 bis zu 20 Mol-%, vorzugsweise 0,1 bis 10 Mol-%, besonders bevorzugt 0,2 bis 5 Mol-%, des Fe2O3 durch die entsprechende molare Menge Cr2O3 ersetzt sind, wobei Me für Magnesium, Calcium, Zink, die auch in beliebigen Kombinationen vorhanden sein können, steht, durch Glühen der entsprechenden Metalloxide oder beim Glühen Metalloxide ergebender Ausgangsstoffe, dadurch gekennzeichnet, daß die Glühung bei Temperaturen von 200 bis 9000C in Gegenwart sauerstoffhaltiger und/oder inerter Gase durchgeführt wird.The present invention also relates to a process for the production of anti-corrosive pigments, consisting of 30 to 70 mol% MeO and 70 to 30 mol% Fe 2 O 3 , 0.1 to 20 mol%, preferably 0.1 to 10 mol%, particularly preferably 0.2 to 5 mol%, of the Fe 2 O 3 have been replaced by the corresponding molar amount of Cr 2 O 3 , Me for magnesium, calcium, zinc, which can also be present in any combination , stands, by annealing the corresponding metal oxides or starting materials resulting from annealing metal oxides, characterized in that the annealing is carried out at temperatures of 200 to 900 ° C. in the presence of oxygen-containing and / or inert gases.
Gegenstand der Erfindung ist ferner die Verwendung der erfindungsgemäßen bzw. erfindungsgemäß hergestellten Pigmente für die Herstellung von Rostschutzfarben auf Basis von Korrosionsschutzanstrichen oder Korrosionsschutzlacken.The invention also relates to the use of the pigments according to the invention or produced according to the invention for the production of anti-rust paints based on anti-corrosion paints or Corrosion protection paints.
Die neuen aktiven Korrosionsschutzpigmente auf Basis Eisenoxid werden so gewählt, daß innige Mischungen von 30 bis 70 Mol-% MeO (Me = Mg, Ca, Zn) oder diese beim Glühen liefernde Verbindungen und 70 bis 30 Mol-% Me2O3 (Me = Fe, Cr, wobei der Chromanteil jedoch maximal bis 20 Mol-% betragen kann) oder beim Glühen Me2Oj liefernde Verbindungen bereitet, anschließend in einem bestimmten Temperaturbereich geglüht, das Glühprodukt intensiv gemahlen, gegebenenfalls noch einmal geglüht, abgekühlt und gemahlen werden.The new active anti-corrosive pigments based on iron oxide are chosen so that intimate mixtures of 30 to 70 mol% MeO (Me = Mg, Ca, Zn) or these compounds, which are produced during annealing, and 70 to 30 mol% Me 2 O 3 (Me = Fe, Cr, although the chromium content can be up to a maximum of 20 mol%) or compounds that provide Me 2 Oj during annealing, then annealed in a certain temperature range, the annealed product intensively ground, if necessary once again annealed, cooled and ground.
Die Glühtemperatur ist von entscheidender Bedeutung für die Eigenschaften der erhaltenen Korrosionsschutzpigmente. Sie liegt zwischen 200 und 9000C, vorzugsweise zwischen 250 und 800° C, besonders bevorzugt zwischen 300 und 6500C. Die Glühdauer liegt in der Regel zwischen 0,1 bis 20, vorzugsweise 0,5 bis 10 Stunden. Die erfindungsgemäßen Korrosionsschutzpigmente zeigen spezifische Oberflächen nach BET, G. Brunauer, P. H. Emmet und H. Teller, J. Amer. Chem. Soc, 60,309 (1938), zwischen I und 30 mVg, vorzugswei-The calcination temperature is of decisive importance for the properties of the anti-corrosive pigments obtained. It is between 200 and 900 0 C, preferably between 250 and 800 ° C, more preferably 300-650 0 C. The annealing time is typically between 0.1 to 20, preferably 0.5 to 10 hours. The anti-corrosive pigments according to the invention show specific surfaces according to BET, G. Brunauer, PH Emmet and H. Teller, J. Amer. Chem. Soc, 60, 309 (1938), between 1 and 30 mVg, preferably
se zwischen I bis 15 mVg,se between I to 15 mVg,
Pie erfincjujigsgemftßen Korrosionsschutzpigmente zeigen nach dem Thomson-Korrosionstest (H, A, Gardener, Physical and Chemical Exminations of Paints, Varnishes, Lacquers and Colors, 11. Auflage, Bethesda, 1950, S. 399) Prozentverluste pro Gramm Pigment von weniger als 0,05% pro Gramm Korrosionsschutzpigment, vorzugsweise weniger als_ 0,03% pro Gramm Korrosionsschutzpigment Im Vergleich zeigt ein Korrosionsschutzpigment auf Basis Pb3O4 nach dem Thomson-Korrosionstest einen Prozentverlust pro Gramm Pb3O4 in der Größenordnung von 0,06%, ein aktives Zinkoxid einen Prozentverlust pro Gramm Zinkoxid in Höhe von 0,08%.According to the Thomson corrosion test (H, A, Gardener, Physical and Chemical Exminations of Paints, Varnishes, Lacquers and Colors, 11th edition, Bethesda, 1950, p. 399), the corrosion protection pigments according to the invention show percentage losses per gram of pigment of less than 0, 05% per gram of anti-corrosive pigment, preferably less than 0.03% per gram of anti-corrosive pigment In comparison, an anti -corrosive pigment based on Pb 3 O 4 according to the Thomson corrosion test shows a percentage loss per gram of Pb3O 4 of the order of magnitude of 0.06%, an active zinc oxide a percent loss per gram of zinc oxide of 0.08%.
Als Ausgangsverbindungen bei der Herstellung der erfindungsgemäßen Korrosionsschutzpigmente können für MeO die zweiwertigen Oxide der Elemente Magnesium, Calcium und Zink bzw. diese beim Glühen liefernde Verbindungen, wie Hydroxide, Hydroxysalze, Carbonate, bauche Carbonate, Nitrate, Chloride, Sulfate, Formiate, Acetate, Oxalate und andere organische Verbindungen dieser zweiwertigen Metalle dienen. Für FeA können beliebige Eisenoxide eingesetzt werden oder beim Glühen dreiwertiges Eisenoxid liefernde Verbindungen, wie Oxidhydroxide, Hydroxide, Hydroxysalze, Carbonate, basische Carbonate, Nitrate, Chloride, Sulfate, Formiate, Acetate, Oxalate. Werden Eisenverbindungen eingesetzt die das Eisen nicht in dreiwertigem Zustand enthalten, so ist die Glühung der erfindungsgemäßen Korrosionsschutzpigmente in sauerstoffhaltiger Atmosphäre, vorzugsweise an Luft oder sauerstoffangereicherter Luft durchzuführen. Als besonders vorteilhaft erweisen siel·, bei den Eisenverbindungen Fe(OH)2, FeCO3 oder basisches Carbonat, die man durch Alkali- oder Erdali.alihydroxid- oder -carbonat-Fällung aus Eisen(II)-salzen, vorzugsweise Eisen(II)-sulfatlösungen gewinnen kann.For MeO, the divalent oxides of the elements magnesium, calcium and zinc or compounds such as hydroxides, hydroxy salts, carbonates, carbonates, nitrates, chlorides, sulfates, formates, acetates, oxalates can be used as starting compounds in the production of the anti-corrosive pigments according to the invention and other organic compounds of these divalent metals. Any iron oxides can be used for FeA or compounds which produce trivalent iron oxide during annealing, such as oxide hydroxides, hydroxides, hydroxy salts, carbonates, basic carbonates, nitrates, chlorides, sulfates, formates, acetates, oxalates. If iron compounds are used which do not contain iron in a trivalent state, the anticorrosive pigments according to the invention are annealed in an oxygen-containing atmosphere, preferably in air or oxygen-enriched air. In the case of the iron compounds Fe (OH) 2, FeCO 3 or basic carbonate, which are obtained by alkali or alkaline earth metal hydroxide or carbonate precipitation from iron (II) salts, preferably iron (II), they prove to be particularly advantageous. -sulphate solutions can win.
Weitere technisch interessante Rohstoffe für Eisen(I I I)-oxid sind die bei der Reduktion aromatischer Nitroverbindungen mit Eisen in saurer Lösung anfallenden Fe3O4-, Λ-FeOOH- und a-Fe2Oj-Pigmentschlämme oder die nach dem Luftoxidationsverfahren mit Eisenschrott oder Fe(OH)2-Fällung in Gegenwart von Keimen darstellbaren Eisenoxidgelb- («-FeOOH), Eisenoxidorange- (y-FeOOH) und Eisenoxidrotpigmente (Λ-FejOj). Auch die aus kristallwasserhaltigem oder kristallwasserfreiem Eisen(II)-sulfat durch Röstoxidations- oder Röstreaktionsverfahren anfallenden roten, braunen und schwarzen Eisenoxide sind für die Herstellung der neuen aktiven Korrosionsschutzpigmente geeignete Ausgangsverbindungen.Other technically interesting raw materials for iron (III) oxide are the Fe 3 O 4 , Λ-FeOOH and a-Fe 2 Oj pigment sludges that are obtained from the reduction of aromatic nitro compounds with iron in acidic solution, or those obtained by the air oxidation process with scrap iron or Fe (OH) 2 precipitation in the presence of germs representable iron oxide yellow («-FeOOH), iron oxide orange (y-FeOOH) and iron oxide red pigments (Λ-FejOj). The red, brown and black iron oxides obtained from iron (II) sulfate containing or free of water of crystallization by roasting oxidation or roasting reaction processes are also suitable starting compounds for the production of the new active anti-corrosive pigments.
Geeignete Chromverbindungen sind die dreiwertigen Oxide oder Oxidhydrate selbst oder die diese beim Glühen liefernden kristallinen oder amorphen Hydroxide, Oxidhydroxide, Oxidaquate, basischen Carbonate, Nitrate, Chloride, Sulfate, Formiate, Acetate, Oxalate usw. Vorzugsweise wird Cr2O3 selbst verwendet.Suitable chromium compounds are the trivalent oxides or hydrated oxides themselves or the crystalline or amorphous hydroxides, oxide hydroxides, oxide equates, basic carbonates, nitrates, chlorides, sulfates, formates, acetates, oxalates, etc. that produce them during annealing . Cr 2 O 3 itself is preferably used.
In einer speziellen Ausführungsform werden Chromat(VI)- oder Dichromatverbindungen, beispielsweise Natriumchromat oder Natriumdichromat, mit Eisen(II)-salzen in geeigneten Mengen unter Reduktion des Cr(VI) zu Cr(III) und gleichzeitiger Oxidation von Fe(II) zu Fe(IU) umgesetzt, wobei eine Mischfällung von Chrom(III)- und Eisen(III)-oxidaquat entsteht. Diese Mischfällung ist ein hervorragend geeignetes Ausgangsmaterial für die Herstellung der erfindungsgemäßen Korrosionsschutzpigmente.In a special embodiment, chromate (VI) or dichromate compounds, for example Sodium chromate or sodium dichromate, with iron (II) salts in suitable amounts with reduction of the Cr (VI) converted to Cr (III) and simultaneous oxidation of Fe (II) to Fe (IU), with a mixed precipitation of Chromium (III) and iron (III) oxide aquat are produced. This mixed precipitation is an excellent starting material for the production of the anti-corrosive pigments according to the invention.
Eine weitere Möglichkeit zur Herstellung der oxidischen Ausgangsstoffe Wr die neuen Korrosionsschutzpigmente besteht in einer vollständigen oder teilweisen gemeinsamen Ausfällung von Me(II)- und Me(IH>SalzIösungen (Me(U) = Mg, Ca, Zn, Fe; Me(UI)5=Fe, Cr) mit Alkali-, Erdalkalihydroxid oder -carbonaten.Another possibility for the production of the oxidic starting materials Wr the new anti-corrosion pigments consists in a complete or partial joint precipitation of Me (II) and Me (IH> salt solutions (Me (U) = Mg, Ca, Zn, Fe; Me (UI)) 5 = Fe, Cr) with alkali, alkaline earth hydroxide or carbonates.
In den nachfolgenden Tabellen 1 bis 3 werden die Eigenschaften verschiedener erfindungsgeniäßer Korrosionsschutzpigmente in Abhängigkeit vor ihrer Zusammensetzung und der Glühtemperatur dargestellt Die Korrosionsschutzpigmente wurden so gewonnen, daß innige Mischungen von 30 bis 70 MoI-% MeO (Me(II) = Mg, Ca, Zn) oder diese beim Glühen liefernde Verbindungen und 70 bis 30 Mol-% Me2O3 (Me(III) =Tables 1 to 3 below show the properties of various anti-corrosion pigments according to the invention as a function of their composition and the calcination temperature. The anti-corrosion pigments were obtained in such a way that intimate mixtures of 30 to 70 mol% MeO (Me (II) = Mg, Ca, Zn ) or these annealing compounds and 70 to 30 mol% Me 2 O 3 (Me (III) =
is Fe, Cr) oder diese beim Glühen liefernde Verbindungen hergestellt eine halbe Stunde auf eine 1000C unterhalb der in den Tabellen 1 bis 3 angegebenen Temperatur erhitzt das Glühprodukt intensiv gemahlen und eine halbe Stunde bei den in den Tabellen angegebenen Endtemperaturen geglüht abgekühlt und gemahlen wurden. Die absoluten Mengen der Glühprodukte bewegten sich im Bereich von 50 bis 100 g. Die Ergebnisse der Pigmentabprüfungen von 30 g finden sich getrennt nach den Systemen MgO · (Fe, Cr)2O3 (Tabelle l),CaO · (Fe, Cr)2O3 (Tabelle 2) und ZnO · (Fe, Cr)2O3 (Tabelle 3) in Abhängigkeit vom Cr2O3-Gehalt und von der Endglühtemperatur. Man erkennt welch starke Verbesserung die die Korrosion verhindernde Wirkung der Pigmente durch den Ersatz eines Teils des Eisen(III)-oxids durch Chrom(III)-oxid erfährt und wie die Glühtemperatur mit steigendem Anteil an Cr2O3 nach höheren Werten verschoben werden kann, ohne daß die gute Qualität der aktiven neuen Korrosionsschutzpigmente abnimmtis Fe Cr), or these compounds delivered during annealing produced a half hour to a 100 0 C below the specified in Tables 1 to 3 temperature, the fired product is heated intensely milled and calcined cooled for half an hour at the indicated in Tables final temperatures and ground became. The absolute quantities of the annealing products ranged from 50 to 100 g. The results of the pigment tests of 30 g can be found separately according to the systems MgO (Fe, Cr) 2 O 3 (Table 1), CaO (Fe, Cr) 2 O 3 (Table 2) and ZnO (Fe, Cr) 2 O 3 (Table 3) as a function of the Cr 2 O 3 content and the final annealing temperature. You can see the great improvement in the corrosion-preventing effect of the pigments by replacing part of the iron (III) oxide with chromium (III) oxide and how the annealing temperature can be shifted to higher values with an increasing proportion of Cr 2 O 3 without reducing the good quality of the active new anti-corrosive pigments
Der Thomsen-Korrosionstest an den Pigmenten wurde wie folgt durchgeführt:The Thomsen corrosion test on the pigments was carried out as follows:
In eine mit doppelt durchbohrtem Stopfen versehene 200-ml-Pulverflasche wurden je nach Schüttgewicht 15 oder 30 g Pigment, 60 ml bidestilliertr-s Wasser und vierIn a 200 ml powder bottle with a double-pierced stopper, depending on the bulk weight, 15 or 30 g pigment, 60 ml double-distilled water and four
gereinigte und mit Äther entfettete, gewogene und mit Perlonfäden festgebundene, glänzend polierte Rasierklingen eingebracht. Durch Glasrohre wurden die einzeln hintereinander gereihten Pulverflaschen mit den verschiedenen Pigmentsuspensionen unter Zwischen-Cleaned, shiningly polished razor blades, degreased with ether, weighed and tied with Perlon threads brought in. The individually lined up powder bottles with the different pigment suspensions with intermediate
<5 schaltung von leeren Pulverflaschen verbunden. Durch Einschalten des Laborvakuums wurde über ein Luftrotameter und einen als Blasenzähler dienenden Erlenmeyerkolben im Verlauf von 20 Tagen ein gleichbleibender Luftstrom von 60 l/h durchgeleitet. Durch diesen Luftstrom wird die Pigmentsuspension ständig durchgewirbelt und kommt das Pigment ständig in Kontakt mit dem Wasser. Nach Ablauf von 20 Tagen wurden die Rasierklingen aus jeder Flasche herausgenommen, sorgfältig gereinigt, getrocknet und der Gewichtsverlust durch Rückwaage bestimmt. Der prozentuale Gewichtsverlust wird durch die eingesetzte Pigmentmenge dividiert. Der Prozentverlust/g Pigment stellt ein Maß für die Stärke der Korrosion dar. Je niedriger dieser Wert ist, um s>o größer ist die die Korrosion verhindernde Wirkung des Pigments. Da die so ermittelten Wert« sehr klein sind, wurden sie zur Vereinfachung einer vergleichenden Betrachtung mit einem Faktor von 103 multipliziert. Diese Werte sind in den letzten Kolonien der Tabellen 1 bis 3 angegeben.<5 circuit of empty powder bottles connected. By switching on the laboratory vacuum, a constant air flow of 60 l / h was passed through an air rotameter and an Erlenmeyer flask serving as a bubble counter over the course of 20 days. The pigment suspension is constantly swirled through this air stream and the pigment comes into constant contact with the water. After 20 days, the razor blades were removed from each bottle, carefully cleaned, dried and the weight loss determined by backweighing. The percentage weight loss is divided by the amount of pigment used. The percentage loss / g pigment is a measure of the strength of the corrosion. The lower this value, the greater the corrosion-preventing effect of the pigment. Since the values determined in this way are very small, they were multiplied by a factor of 10 3 to simplify a comparative analysis. These values are given in the last colonies in Tables 1 to 3.
<" Zum Vergleich mit den erfindungsgemäßen Korrosionsschutzpigmenten ist in der Tabelle 4 das Korrosionsverhalten von einigen anorganischen Pigmenten beim Thomson-Kcrrosionstest dargestellt.<"For comparison with the anti-corrosion pigments according to the invention Table 4 shows the corrosion behavior of some inorganic pigments shown in the Thomson corrosion test.
Korrosionsverhalten einiger MgO und (Fe, Cr)2O3 enthaltender Pigmente in Abhängigkeit von der Glühtemperatur (30 g Pigment/60 ml H2O)Corrosion behavior of some pigments containing MgO and (Fe, Cr) 2 O 3 as a function of the annealing temperature (30 g pigment / 60 ml H 2 O)
Vers. Zusammensetzung Nr, in Mol-%Vers. Composition No., in mol%
CaO Fe3O., Cr2O3 CaO Fe 3 O., Cr 2 O 3
temperatur lusi/g Pjg-'/2 \\- C menttemperature lusi / g Pjg - '/ 2 \\ - C ment
Vers. Zusammensetzung Nr. in Mol-%Vers. Composition No. in mol%
MgO Fe2O3 Cr2O3 MgO Fe 2 O 3 Cr 2 O 3
Glühtemperatur '/2h-'CAnnealing temperature '/ 2h-'C
103x%-Verlust/g Pigment10 3 x% loss / g pigment
1.12
1.13
1.14
1.15
1.16
1.171.12
1.13
1.14
1.15
1.16
1.17
50,0
50,0
50,0
50,0
50,050.0
50.0
50.0
50.0
50.0
50,0
50,0
50,0
50,0
50,0
50,050.0
50.0
50.0
50.0
50.0
50.0
50,0
50,0
50,0
50,0
50,0
50,050.0
50.0
50.0
50.0
50.0
50.0
50,0
50,0
50,0
50,0
50,0
50,050.0
50.0
50.0
50.0
50.0
50.0
50,0
50,0
50,0
50,0
50,0
50,050.0
50.0
50.0
50.0
50.0
50.0
49,3
49J
49,3
49,3
49,349.3
49J
49.3
49.3
49.3
48,7
48,7
48,7
48,7
48,7
48,748.7
48.7
48.7
48.7
48.7
48.7
47,1
47,1
47,1
47,1
47,1
47,147.1
47.1
47.1
47.1
47.1
47.1
44,2
44,2
44,2
44,2
44,2
44,244.2
44.2
44.2
44.2
44.2
44.2
0,7
0,7
0,7
0,7
0,70.7
0.7
0.7
0.7
0.7
1,3
1,3
1,3
1,3
1,3
1,31.3
1.3
1.3
1.3
1.3
1.3
2,9
2,9
2,9
2,9
2,9
2,92.9
2.9
2.9
2.9
2.9
2.9
5,8
5,8
5,8
5,8
5,8
5,85.8
5.8
5.8
5.8
5.8
5.8
41,0 9,041.0 9.0
41,0 9,041.0 9.0
41,0 9,041.0 9.0
41,0 9,041.0 9.0
41,0 9,041.0 9.0
41,0 9,041.0 9.0
300
400
500
600
700300
400
500
600
700
300
400
500
600
700
800300
400
500
600
700
800
300
400
500
600
700
800300
400
500
600
700
800
300
400
500
600
700
800300
400
500
600
700
800
300
400
JOO
600
700
800300
400
JOO
600
700
800
0,30 0,00 0,15 3,44 6,200.30 0.00 0.15 3.44 6.20
0,00 0,00 0,00 1,35 3,44 4,920.00 0.00 0.00 1.35 3.44 4.92
0,87 0,58 0,00 0,00 0,00 4,070.87 0.58 0.00 0.00 0.00 4.07
0,15 0,00 0,00 0,44 0,15 4,650.15 0.00 0.00 0.44 0.15 4.65
1,90 0,29 0,72 0,00 0,29 1,601.90 0.29 0.72 0.00 0.29 1.60
IOIO
1515th
2020th
2,82.8
2.92.9
2.102.10
2.112.11
2.122.12
2.132.13
2.14 2.15 2.16 2.17 2.18 2.19 2.20 2.212.14 2.15 2.16 2.17 2.18 2.19 2.20 2.21
2.22 2.23 2.24 2.252.22 2.23 2.24 2.25
3535
2.26 2.27 2.28 40 2.29 2.302.26 2.27 2.28 40 2.29 2.30
30 50,0
50,0
50,030 50.0
50.0
50.0
50,0
50,0
50,0
50,0
50,0
50,050.0
50.0
50.0
50.0
50.0
50.0
50,0
50,0
50,0
50,0
50,0
50,0
50,0
50,050.0
50.0
50.0
50.0
50.0
50.0
50.0
50.0
50,0
50,0
50,0
50,050.0
50.0
50.0
50.0
50,0
50,0
50,0
50,0
50,050.0
50.0
50.0
50.0
50.0
49,1
49,1
49,149.1
49.1
49.1
48,3
48,3
48,3
48,3
48,3
48,348.3
48.3
48.3
48.3
48.3
48.3
47,4
47,4
47,4
47,4
47,4
47,4
47,4
47,447.4
47.4
47.4
47.4
47.4
47.4
47.4
47.4
43,9
43,9
43,9
43,943.9
43.9
43.9
43.9
37,7
37,7
37,7
37,7
37,737.7
37.7
37.7
37.7
37.7
0,9
0,9
0,90.9
0.9
0.9
1,7
1,7
1,7
1,7
1,7
1,71.7
1.7
1.7
1.7
1.7
1.7
2,6
2,6
2,6
2,6
2,6
2,6
2,6
2,62.6
2.6
2.6
2.6
2.6
2.6
2.6
2.6
6,1
6,1
6,1
6,16.1
6.1
6.1
6.1
12,3
12,3
12,3
12,3
12,312.3
12.3
12.3
12.3
12.3
700
750
800700
750
800
500
600
700
750
800
850500
600
700
750
800
850
500
550
600
650
700
750
800
850500
550
600
650
700
750
800
850
500
600
700
800500
600
700
800
500
600
650
700
750500
600
650
700
750
0,30 0,45 2,720.30 0.45 2.72
0,00 0,00 0,OL 0,00 0,00 0,300.00 0.00 0, OL 0.00 0.00 0.30
0,15 0,15 0,14 0,00 0,29 0,15 0,58 0,430.15 0.15 0.14 0.00 0.29 0.15 0.58 0.43
1,94 1,82 2,10 6,881.94 1.82 2.10 6.88
0,43 0,00 0,00 0,70 1,450.43 0.00 0.00 0.70 1.45
45 Tabelle 45 table Korrosionsverhalten einiger ZnO und (Fe, Cr)2O3 enthaltender Pigmente in Abhängigkeit von der Glühtemperatur (30 g Pigment/60 ml H2O)Corrosion behavior of some ZnO and (Fe, Cr) 2 O 3 containing pigments as a function of the annealing temperature (30 g pigment / 60 ml H 2 O)
5050
Fortsetzungcontinuation
Vers. Zusammensetzung Ciliih-Vers. Composition Ciliih-
Nr. in Mol-"',, temperaturNo. in mole temperature
ZnO FcO1 Cr,O,ZnO FcO 1 Cr, O,
3.10 50,03.10 50.0
3.11 50,03.11 50.0
3.12 50,03.12 50.0
3.13 50,03.13 50.0
3.14 50,03.14 50.0
3.15 50,03.15 50.0
3.16 50,03.16 50.0
3.17 50,03.17 50.0
50,0
50,0
50,0
50,0
50,0
50,050.0
50.0
50.0
50.0
50.0
50.0
47,3 47,3 47,347.3 47.3 47.3
44.1 44,1 44,1 44,1 44.144.1 44.1 44.1 44.1 44.1
38.3 38,3 38,3 38.3 38.3 38,338.3 38.3 38.3 38.3 38.3 38.3
3.24 50,0 31,93.24 50.0 31.9
3.25 50,0 31,93.25 50.0 31.9
3.26 50,0 31.93.26 50.0 31.9
2,7 2,7 2,72.7 2.7 2.7
5,9 5,9 5.9 5.9 5,95.9 5.9 5.9 5.9 5.9
11.7 11.7 11.7 11.7 11.7 11.711.7 11.7 11.7 11.7 11.7 11.7
18,1 18,1 18.118.1 18.1 18.1
101 x %-Verlust/g Pigment 10 1 x% loss / g pigment
Vers.Verse.
Nr.No.
500 600500 600
700700
300 400 500 600 700300 400 500 600 700
250 300 400 500 600 700250 300 400 500 600 700
250 300 400250 300 400
0,00 14,11 25,79 0.00 14.11 25.79
3,44 0,00 0,00 1,63 3,913.44 0.00 0.00 1.63 3.91
7,32 6,53 0,00 0,15 1.74 5,517.32 6.53 0.00 0.15 1.74 5.51
11.79 1.31 0,0011.79 1.31 0.00
Zusammensetzung
in Mol-".,composition
in moles ".,
Ciliihlemperatur Cold temperature
lO'xWcf. lust/g Pigment lO'xWcf. lust / g pigment
ZnOZnO
Cr1O-,Cr 1 O-,
3.27 50,0 31,9 18,1 500 0,003.27 50.0 31.9 18.1 500 0.00
3.28 50,0 31,9 18,1 600 1,61 3.28 50.0 31.9 18.1 600 1.61
3.29 50,0 31.9 18.1 700 6.15 3.29 50.0 31.9 18.1 700 6.15
Korrosionsverhalten von einigen anorganischen Pigmenten beim Thomson-TestCorrosion behavior of some inorganic pigments in the Thomson test
Nr.Verse.
No.
ments TypKind of Pig
ments type
60 ml HiOg pigment /
60 ml HiO
(%)loss
(%)
lust/g Pig
mentΙ0 · 'χ Wer-
lust / g Pig
ment
Claims (4)
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2537684A DE2537684C3 (en) | 1975-08-23 | 1975-08-23 | Active anti-corrosive pigments based on iron oxide |
| US05/713,480 US4140538A (en) | 1975-08-23 | 1976-08-11 | Iron oxide-based anti-corrosion pigments |
| GB34191/76A GB1551446A (en) | 1975-08-23 | 1976-08-17 | Iron oxide-based anti-corrosion pigments |
| JP51098845A JPS5226530A (en) | 1975-08-23 | 1976-08-20 | Anti corrosive pigments and method of their preparation |
| IT50968/76A IT1062675B (en) | 1975-08-23 | 1976-08-20 | IRON OXIDE BASED ANTI-CORROSION PIGMENTS AND PROCEDURE TO PRODUCE THEM |
| FR7625499A FR2322181A1 (en) | 1975-08-23 | 1976-08-23 | ANTI-CORROSION PIGMENT BASED ON IRON OXIDE AND ITS PREPARATION PROCESS |
| US05/923,517 US4211565A (en) | 1975-08-23 | 1978-07-10 | Iron oxide-based anti-corrosion pigments |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2537684A DE2537684C3 (en) | 1975-08-23 | 1975-08-23 | Active anti-corrosive pigments based on iron oxide |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| DE2537684A1 DE2537684A1 (en) | 1977-03-03 |
| DE2537684B2 DE2537684B2 (en) | 1979-11-29 |
| DE2537684C3 true DE2537684C3 (en) | 1980-07-31 |
Family
ID=5954737
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE2537684A Expired DE2537684C3 (en) | 1975-08-23 | 1975-08-23 | Active anti-corrosive pigments based on iron oxide |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US4140538A (en) |
| JP (1) | JPS5226530A (en) |
| DE (1) | DE2537684C3 (en) |
| FR (1) | FR2322181A1 (en) |
| GB (1) | GB1551446A (en) |
| IT (1) | IT1062675B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2625401A1 (en) * | 1976-06-05 | 1977-12-22 | Bayer Ag | Non-corrosive pigments - are composed of oxides of calcium, iron, aluminium and manganese |
| DE2642049A1 (en) * | 1976-09-18 | 1978-03-23 | Bayer Ag | Anticorrosive pigment compsns. based on iron oxide - contg. specified metal oxide(s), used in lacquers and varnishes |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4156613A (en) * | 1976-06-05 | 1979-05-29 | Bayer Aktiengesellschaft | Anti-corrosion pigments |
| DE2904491A1 (en) * | 1979-02-07 | 1980-08-21 | Bayer Ag | PLATE-SHAPED IRON OXIDE PIGMENTS AND METHOD FOR THE PRODUCTION AND USE THEREOF |
| DE3411215A1 (en) * | 1984-03-27 | 1985-10-10 | Basf Ag, 6700 Ludwigshafen | METHOD FOR PRODUCING TRANSPARENT GOLD-YELLOW, TEMPERATURE-STABLE TWO-PHASE PIGMENTS OF THE GENERAL FORMULA XZNO.ZNFE (DOWN ARROW) 2 (DOWN ARROW) O (DOWN ARROW) 4 (DOWN ARROW) |
| DE4131548A1 (en) * | 1991-09-21 | 1993-03-25 | Degussa | BROWN SPINEL COLOR BODIES ON THE BASIS OF ZINC CHROMITE, PROCESS FOR THEIR PRODUCTION AND THEIR USE |
| CA2453005A1 (en) * | 2003-12-17 | 2005-06-17 | Fermag Inc. | Hydrometallurgical process for separating steel mill dust using an arc furnace and pigments obtained by the process |
| CA2611197A1 (en) * | 2005-06-17 | 2006-12-21 | Ferrinov Inc. | Anti-corrosion pigments coming from dust of an electic arc furnace and containing sacrificial calcium |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE728974C (en) * | 1939-11-23 | 1942-12-08 | Degussa | Improvement of chromium-containing colored bodies |
| US2416064A (en) * | 1943-04-28 | 1947-02-18 | Du Pont | Chromite ore pigment |
| US2502130A (en) * | 1947-08-29 | 1950-03-28 | Columbian Carbon | Preparation of magnesium ferrite pigment |
| US2904395A (en) * | 1955-02-24 | 1959-09-15 | Columbian Carbon | Method for producing zinc ferrite pigment |
| GB916281A (en) * | 1960-12-29 | 1963-01-23 | Ferro Corp | Colours for glazes suspended in resins |
| JPS5040419B2 (en) * | 1972-08-30 | 1975-12-24 | ||
| JPS5317618B2 (en) * | 1972-09-13 | 1978-06-09 | ||
| US3832455A (en) * | 1972-10-25 | 1974-08-27 | Smith G Labor | Preparation of zinc ferrite yellow pigments |
| JPS5317619B2 (en) * | 1972-10-26 | 1978-06-09 |
-
1975
- 1975-08-23 DE DE2537684A patent/DE2537684C3/en not_active Expired
-
1976
- 1976-08-11 US US05/713,480 patent/US4140538A/en not_active Expired - Lifetime
- 1976-08-17 GB GB34191/76A patent/GB1551446A/en not_active Expired
- 1976-08-20 JP JP51098845A patent/JPS5226530A/en active Pending
- 1976-08-20 IT IT50968/76A patent/IT1062675B/en active
- 1976-08-23 FR FR7625499A patent/FR2322181A1/en active Granted
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2625401A1 (en) * | 1976-06-05 | 1977-12-22 | Bayer Ag | Non-corrosive pigments - are composed of oxides of calcium, iron, aluminium and manganese |
| DE2642049A1 (en) * | 1976-09-18 | 1978-03-23 | Bayer Ag | Anticorrosive pigment compsns. based on iron oxide - contg. specified metal oxide(s), used in lacquers and varnishes |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5226530A (en) | 1977-02-28 |
| FR2322181A1 (en) | 1977-03-25 |
| GB1551446A (en) | 1979-08-30 |
| DE2537684B2 (en) | 1979-11-29 |
| FR2322181B1 (en) | 1980-05-23 |
| IT1062675B (en) | 1984-10-20 |
| US4140538A (en) | 1979-02-20 |
| DE2537684A1 (en) | 1977-03-03 |
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